WO2010013420A1 - 化合物、重合性組成物、樹脂、およびその使用 - Google Patents

化合物、重合性組成物、樹脂、およびその使用 Download PDF

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Publication number
WO2010013420A1
WO2010013420A1 PCT/JP2009/003480 JP2009003480W WO2010013420A1 WO 2010013420 A1 WO2010013420 A1 WO 2010013420A1 JP 2009003480 W JP2009003480 W JP 2009003480W WO 2010013420 A1 WO2010013420 A1 WO 2010013420A1
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group
bis
compound
general formula
polymerizable composition
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PCT/JP2009/003480
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English (en)
French (fr)
Japanese (ja)
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村上正和
安藤知行
小林誠一
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三井化学株式会社
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Priority to CN200980129004.7A priority Critical patent/CN102105478B/zh
Priority to KR1020117001367A priority patent/KR101290929B1/ko
Priority to US13/055,280 priority patent/US8349996B2/en
Priority to JP2010522604A priority patent/JP5442614B2/ja
Priority to EP09802669.3A priority patent/EP2311845B1/de
Publication of WO2010013420A1 publication Critical patent/WO2010013420A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/06—Polythioethers from cyclic thioethers
    • C08G75/08—Polythioethers from cyclic thioethers from thiiranes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/90—Antimony compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/005—Compounds of elements of Group 5 of the Periodic Table without metal-carbon linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/94—Bismuth compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/06—Polythioethers from cyclic thioethers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

Definitions

  • the present invention relates to a compound, a polymerizable composition, a resin, and use thereof.
  • transparent organic polymer materials have been used as transparent materials to replace inorganic glass.
  • an optical resin for example, it is generally required to have a high refractive index while having generally required characteristics such as transparency, thermal characteristics, and mechanical characteristics.
  • M 1 is Sb or Bi, and X 1 and X 2 are each independently a sulfur atom or an oxygen atom.
  • R 1 is a divalent organic group
  • Y 1 Is a monovalent inorganic or organic group.
  • a is 1 or 2.
  • b is 0 or an integer of 1 or more.
  • c is an integer of 1 or more and d or less.
  • d is the valence of M 1.
  • the plurality of Y 1 are each independently a monovalent inorganic or organic group. At this time, a plurality of Y 1 may be bonded to each other to form a ring containing M 1 .
  • e is 0 or an integer of 1 or more.
  • M 1 is Sb or Bi
  • X 1 and X 2 are each independently a sulfur atom or an oxygen atom.
  • R 1 is a divalent organic group
  • Y 1 Is a monovalent inorganic or organic group.
  • b is 0 or an integer of 1 or more.
  • c is an integer of 1 or more and d or less.
  • d is the valence of M 1.
  • the plurality of Y 1 are each independently a monovalent inorganic or organic group. At this time, a plurality of Y 1 may be bonded to each other to form a ring containing M 1 .
  • M 2 is a metal atom.
  • X 3 and X 4 are each independently a sulfur atom or an oxygen atom.
  • R 2 is a divalent organic group.
  • m is 0 or an integer of 1 or more.
  • n is the valence of M 2
  • p is an integer not less than 1 or more n.
  • q is 0 or an integer of 1 to n-2.
  • Y 2 is a monovalent or divalent group
  • T is an inorganic or organic group.
  • a plurality of Y 2 may be bonded to each other to form a ring containing the metal atom M 2 .
  • npq 1 or 2
  • Y 2 is a divalent group.
  • two Y 2 may form a ring together with two metal atoms M 2 .
  • the plurality of T are each independently an inorganic or organic group.
  • a method for producing a resin comprising a step of cast polymerization of the polymerizable composition according to any one of [7] to [14].
  • a novel compound for obtaining a transparent resin having a high refractive index is provided.
  • the organic group may contain hetero atoms other than a carbon atom and a hydrogen atom in the group.
  • the hetero atom include an oxygen atom, a sulfur atom and a nitrogen atom.
  • the present invention relates to a compound having a cyclic structure containing S in the molecule and having an Sb atom or a Bi atom.
  • the present invention relates to a compound represented by the following general formula (1). This compound is suitable for optical components.
  • M 1 is a Sb or Bi
  • X 1 and X 2 are the .R 1 are each independently a sulfur atom or an oxygen atom, a divalent organic group
  • Y 1 is a monovalent Inorganic or organic groups.
  • a is 1 or 2.
  • b is 0 or an integer of 1 or more.
  • c is an integer of 1 or more and d or less.
  • d is the valence of M 1.
  • the plurality of Y 1 are each independently a monovalent inorganic or organic group. At this time, a plurality of Y 1 may be bonded to each other to form a ring containing M 1 .
  • e is 0 or an integer of 1 or more.
  • e is preferably 1 from the viewpoint of increasing the refractive index and stability of the compound, and the above general formula (1) is represented by the following general formula (6).
  • a transparent resin having a high refractive index By polymerizing the compound represented by the general formula (1), a transparent resin having a high refractive index can be obtained.
  • R 1 represents a divalent organic group.
  • a divalent organic group include a chain or cyclic aliphatic group, an aromatic group, and an aromatic-aliphatic group. From the viewpoint of increasing the refractive index, preferably the number of carbon atoms is 1 or more and 20 or less.
  • R 1 is such that the divalent organic group is a chain or cyclic aliphatic group, an aromatic group or an aromatic-aliphatic group, Methylene, ethylene, 1,2-dichloroethylene, trimethylene, tetramethylene, pentamethylene, cyclopentylene, hexamethylene, cyclohexylene, heptamethylene, octamethylene, nonamethylene, decamethylene
  • a substituted or unsubstituted chain or cyclic aliphatic group having 1 to 20 carbon atoms such as, undecamethylene group, dodecamethylene group, tridecamethylene group, tetradecamethylene group, pentadecamethylene group, etc .
  • a substituted or unsubstituted aromatic group having 5 to 20 carbon atoms such as a phenylene group, a chlorophenylene group, a naphthylene group, an indenylene group, an anthracenylene group, a fluorenylene group; or a
  • R 1 is more preferably a substituted or unsubstituted chain or cyclic fatty acid having 1 to 6 carbon atoms such as methylene group, ethylene group, 1,2-dichloroethylene group, trimethylene group, cyclopentylene group, cyclohexylene group, etc.
  • a substituted or unsubstituted aromatic group having 5 to 15 carbon atoms such as a phenylene group, a chlorophenylene group, a naphthylene group, an indenylene group, an anthracenylene group, a fluorenylene group; or a —C 6 H 4 —CH 2 — group, —CH 2 —C 6 H 4 —CH 2 — group, —CH 2 —C 6 H 3 (Cl) —CH 2 — group, —C 10 H 6 —CH 2 — group, —CH 2 —C 10 H 6 —CH
  • a substituted or unsubstituted aromatic-aliphatic group having 6 to 15 carbon atoms such as a 2 -group and a —CH 2 CH 2 —C 6 H 4 —CH 2 CH 2 — group.
  • Such a divalent organic group may contain a hetero atom other than a carbon atom or a hydrogen atom in the group.
  • a hetero atom include an oxygen atom or a sulfur atom, but a sulfur atom is preferable in consideration of a desired effect of the present invention.
  • M 1 is Sb or Bi. Regardless of whether M 1 is Bi or Sb, the general formula (1) can improve the refractive index. Sb or Bi is trivalent or pentavalent, but from the viewpoint of increasing the refractive index, Sb or Bi is preferably trivalent. Among these, from the viewpoint of ease of production of the compound and stability of the compound , M 1 is preferably an Sb atom. In the general formula (1), when e is 1 and a is 1, the general formula (1) becomes the following general formula (2).
  • X 1 , X 2 , R 1 , Y 1 , M 1 , b, c, and d are respectively X 1 , X 2 , R 1 , Y in the general formula (1). 1 , M 1 , b, c and d are the same.
  • the general formula (2) is represented by the following general formula (7).
  • Y 1 , M 1 , c, and d are the same as Y 1 , M 1 , c, and d in the general formula (1), respectively.
  • M 1 is the same as M 1 in the general formula (1).
  • X 1 , X 2 , R 1 , Y 1 , M 1 , b, c, d, e are respectively X 1 , X 2 , R 1 in the general formula (1). , Y 1 , M 1 , b, c, d, and e.
  • M 1 , Y 1 , c, and d are the same as M 1 , Y 1 , c, and d in the general formula (1), respectively.
  • Y 1 is a monovalent inorganic or organic group.
  • Y 1 is not particularly limited, and examples thereof include a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, and a substituted group.
  • an unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylthio group is mentioned.
  • a halogen atom a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkoxy (alkyloxy) group, a substituted or unsubstituted alkylthio group
  • the substituted or unsubstituted aryloxy group and the substituted or unsubstituted arylthio group will be described below.
  • Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • substituted or unsubstituted alkyl group include straight chain having 1 to 10 carbon atoms in total such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, etc.
  • An alkyl group Isopropyl, isobutyl, sec-butyl, isopentyl, sec-pentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2- Ethylbutyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group 1-n-propylbutyl group, 1-iso-propylbutyl group, 1-iso-propyl-2-methylpropyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methyl Heptyl, 5-methylheptyl, 6-methylheptyl, 1-ethylhexyl, 2-ethyl
  • substituted or unsubstituted aryl group include an aromatic hydrocarbon group having a total carbon number of 20 or less, such as a phenyl group, a naphthyl group, an anthranyl group, and a cyclopentadienyl group; 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-ethylphenyl group, propylphenyl group, butylphenyl group, hexylphenyl group, cyclohexylphenyl group, octylphenyl group, 2-methyl-1- Naphthyl group, 3-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 5-methyl-1-naphthyl group, 6-methyl-1-naphthyl group, 7-methyl-1-naphthyl group, 8- Methyl-1-naphthyl group, 1-methyl-2-n
  • substituted or unsubstituted aralkyl group examples include aralkyl groups having a total carbon number of 12 or less, such as a benzyl group, a phenethyl group, a phenylpropyl group, and a naphthylethyl group.
  • Other examples include a methyl group, an ethyl group, and a propyl group having an aryl group as a side chain in the specific examples of the substituted or unsubstituted aryl group.
  • substituted or unsubstituted alkyloxy group examples include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, tert-butoxy group, n-pentyloxy group, iso-pentyloxy, n-hexyloxy, iso-hexyloxy, 2-ethylhexyloxy, 3,5,5-trimethylhexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy
  • substituted or unsubstituted alkylthio group examples include methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, t-butylthio group, n- Pentylthio group, iso-pentylthio group, n-hexylthio group, iso-hexylthio group, 2-ethylhexylthio group, 3,5,5-trimethylhexylthio group, n-heptylthio group, n-octylthio group, n-nonylthio group, etc.
  • An alkoxyalkylthio group having 2 to 10 carbon atoms in total such as a thio group, an iso-pentyloxyethylthio group, an n-hexyloxyethylthio group, an iso-hexyloxyethylthio group
  • substituted or unsubstituted aryloxy group examples include phenyloxy group, naphthyloxy group, anthranyloxy group, 2-methylphenyloxy group, 3-methylphenyloxy group, 4-methylphenyloxy group, 2-ethyl Phenyloxy group, propylphenyloxy group, butylphenyloxy group, hexylphenyloxy group, cyclohexylphenyloxy group, octylphenyloxy group, 2-methyl-1-naphthyloxy group, 3-methyl-1-naphthyloxy group, 4 -Methyl-1-naphthyloxy group, 5-methyl-1-naphthyloxy group, 6-methyl-1-naphthyloxy group, 7-methyl-1-naphthyloxy group, 8-methyl-1-naphthyloxy group, -Methyl-2-naphthyloxy group,
  • substituted or unsubstituted arylthio group examples include a phenylthio group, a naphthylthio group, an anthranylthio group, a 2-methylphenylthio group, a 3-methylphenylthio group, a 4-methylphenylthio group, and a 2-ethylphenylthio group.
  • alkoxyarylthio group 2,3-dimethoxyphenylthio group, 2,4-dimethoxyphenylthio group, 2,5-dimethoxyphenylthio group, 2,6-dimethoxyphenylthio group, 3,4-dimethoxyphenylthio group, 3,5-dimethoxy Phenylthio group, 3,6-dimethoxyphenylthio group, 4,5-dimethoxy-1-naphthylthio group, 4,7-dimethoxy-1-naphthylthio group, 4,8-dimethoxy-1-naphthylthio group, 5,8- A dialkoxyarylthio group having a total carbon number of 20 or less substituted by a substituted or unsubstituted alkyloxy group having a carbon number of 10 or less, such as a dimethoxy-1-naphthylthio group or a 5,8-dimethoxy-2-naph
  • Y 1 Preferred examples of such Y 1 are shown below.
  • a preferred example is a hydrogen atom.
  • Y 1 as a halogen atom, a chlorine atom, a bromine atom, an iodine atom.
  • a substituted or unsubstituted alkyl group a linear alkyl group having 1 to 6 carbon atoms in total, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group; Isopropyl, isobutyl, sec-butyl, isopentyl, sec-pentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2- Total carbon number of ethylbutyl group, tert-butyl group, tert-pentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,
  • An aromatic hydrocarbon group having a total carbon number of 12 or less such as a phenyl group, a naphthyl group, a cyclopentadienyl group, as a substituted or unsubstituted aryl group; 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-ethylphenyl group, propylphenyl group, butylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2, 5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,6-dimethylphenyl group, 2,3,4-trimethylphenyl group, 2, 3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,5-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, etc.
  • alkyl-substituted aryl group having 12 or less carbon atoms Substituted or unsubstituted alkyloxy groups having 6 or less carbon atoms such as 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-ethoxyphenyl group, propoxyphenyl group, butoxyphenyl group, etc.
  • Examples of the substituted or unsubstituted aralkyl group include aralkyl groups having a total carbon number of 12 or less, such as a benzyl group, a phenethyl group, and a phenylpropyl group.
  • alkyloxy group methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, tert-butoxy group, n-pentyloxy group, iso-pentyl
  • a cycloalkoxy group having 5 or 6 carbon atoms in total such as a cyclopentyloxy group and a cyclohexyloxy group; and a methoxymethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, an n-propoxymethoxy group, an iso-propoxymethoxy group, and an n-propoxyethoxy group
  • alkoxy-alkoxy groups having 2 to 6 carbon atom
  • alkylthio group methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, a linear or branched alkylthio group having 1 to 6 carbon atoms in total, such as an iso-pentylthio group, an n-hexylthio group, an iso-hexylthio group;
  • a cycloalkylthio group having 5 or 6 carbon atoms in total such as a cyclopentylthio group and a cyclohexylthio group; Total carbon number of 2 such as methoxyethylthio group, ethoxyethylthio group, n-propoxyethylthio group,
  • aryloxy group As a substituted or unsubstituted aryloxy group, phenyloxy group, naphthyloxy group, 2-methylphenyloxy group, 3-methylphenyloxy group, 4-methylphenyloxy group, 2-ethylphenyloxy group, propylphenyloxy group Butylphenyloxy group, hexylphenyloxy group, cyclohexylphenyloxy group, 2,4-dimethylphenyloxy group, 2,5-dimethylphenyloxy group, 2,6-dimethylphenyloxy group, 3,4-dimethylphenyloxy group Group, 3,5-dimethylphenyloxy group, 3,6-dimethylphenyloxy group, 2,3,4-trimethylphenyloxy group, 2,3,5-trimethylphenyloxy group, 2,3,6-trimethylphenyl Oxy group, 2,4,5-trimethylphenyloxy group, 2, , 6-trimethylphenyl group, 3,4,5-trimethylphenyl un
  • arylthio group As a substituted or unsubstituted arylthio group, phenylthio group, naphthylthio group, 2-methylphenylthio group, 3-methylphenylthio group, 4-methylphenylthio group, 2-ethylphenylthio group, propylphenylthio group, butylphenyl Thio group, hexylphenylthio group, cyclohexylphenylthio group, 2,4-dimethylphenylthio group, 2,5-dimethylphenylthio group, 2,6-dimethylphenylthio group, 3,4-dimethylphenylthio group, 3 , 5-dimethylphenylthio group, 3,6-dimethylphenylthio group, 2,3,4-trimethylphenylthio group, 2,3,5-trimethylphenylthio group, 2,3,6-trimethylphenylthio group, 2,4,5-trimethylphenylthi
  • Y 1 A more preferable example of Y 1 is shown below. More preferred examples of Y 1, for example, be mentioned a hydrogen atom. Moreover, a chlorine atom and a bromine atom are mentioned as a halogen atom.
  • substituted or unsubstituted alkyl group examples include linear or branched alkyl groups having 1 to 3 carbon atoms in total, such as a methyl group, an ethyl group, and an iso-propyl group.
  • An aromatic hydrocarbon group having a total carbon number of 12 or less such as a phenyl group, a naphthyl group, a cyclopentadienyl group, as a substituted or unsubstituted aryl group; 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-ethylphenyl group, propylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl
  • An alkyl-substituted aryl group having a total carbon number of 9 or less such as a group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,6-dimethylphenyl group; 9 or less total carbon atoms substituted by substituted or unsubstituted alkyloxy groups having 3 or less carbon atoms such as 2-methoxyphenyl group, 3-
  • monoaryloxyaryl groups having a total carbon number of 12 or less substituted with halogen atoms such as chlorophenyl group, dichlorophenyl group, trichlorophenyl group, bromophenyl group, dibromophenyl group, chloronaphthyl group, bromonaphthyl group, etc. .
  • Examples of the substituted or unsubstituted aralkyl group include aralkyl groups having a total carbon number of 9 or less, such as a benzyl group, a phenethyl group, and a phenylpropyl group.
  • a substituted or unsubstituted alkyloxy group a straight-chain or branched alkoxy group having 1 to 3 carbon atoms in total such as a methoxy group, an ethoxy group, and an iso-propoxy group; and a total carbon such as a cyclopentyloxy group and a cyclohexyloxy group
  • the cycloalkoxy group of number 5 or 6 is mentioned.
  • a linear or branched alkylthio group having 1 to 3 carbon atoms in total such as a methylthio group, an ethylthio group, an n-propylthio group, an iso-propylthio group, as a substituted or unsubstituted alkylthio group;
  • a cycloalkylthio group having 5 or 6 carbon atoms in total such as a cyclopentylthio group and a cyclohexylthio group; and a methylthioethylthio group, an ethylthioethylthio group, an n-propylthioethylthio group, an iso-propylthioethylthio group, an n- Examples thereof include an alkylthioalkylthio group having 2 to 6 carbon atoms in total, such as a butylthioethylthio group, an iso-butylthioe
  • aryloxy group As a substituted or unsubstituted aryloxy group, phenyloxy group, naphthyloxy group, 2-methylphenyloxy group, 3-methylphenyloxy group, 4-methylphenyloxy group, 2-ethylphenyloxy group, propylphenyloxy group 2,4-dimethylphenyloxy group, 2,5-dimethylphenyloxy group, 2,6-dimethylphenyloxy group, 3,4-dimethylphenyloxy group, 3,5-dimethylphenyloxy group, 3,6- An unsubstituted or alkyl-substituted aryloxy group having a total carbon number of 9 or less, such as a dimethylphenyloxy group; Substituted or unsubstituted alkyloxy groups having 3 or less carbon atoms such as 2-methoxyphenyloxy group, 3-methoxyphenyloxy group, 4-methoxyphenyloxy group, 2-ethoxyphenyloxy group
  • Examples include substituted aryloxy groups having 12 or less carbon atoms.
  • arylthio group As a substituted or unsubstituted arylthio group, phenylthio group, 2-methylphenylthio group, 3-methylphenylthio group, 4-methylphenylthio group, 2-ethylphenylthio group, propylphenylthio group, 2,4-dimethyl Phenylthio group, 2,5-dimethylphenylthio group, 2,6-dimethylphenylthio group, 3,4-dimethylphenylthio group, 3,5-dimethylphenylthio group, 3,6-dimethylphenylthio group, etc.
  • Substituted or unsubstituted alkyloxy groups having 3 or less carbon atoms such as 2-methoxyphenylthio group, 3-methoxyphenylthio group, 4-methoxyphenylthio group, 2-ethoxyphenylthio group, propoxyphenylthio group A monoalkoxyarylthio group having a total carbon number of 9 or less; and halogen atoms such as chlorophenylthio group, dichlorophenylthio group, trichlorophenylthio group, bromophenylthio group, dibromophenylthio group, chloronaphthylthio group, bromonaphthylthio group A substituted arylthio group having a total carbon number of 12 or less is exemplified.
  • Y 1 is more specifically represented by an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group: a methylthio group, an ethylthio group, n And straight-chain or branched alkylthio groups having a sulfur atom directly bonded to M 1 atom and having a total carbon number of 1 to 3, such as -propylthio group and iso-propylthio group.
  • an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group: a methylthio group, an ethylthio group, n And straight-chain or branched alkylthio groups having a sulfur atom directly bonded to M 1 atom and having a total carbon number of 1 to 3, such as -propylthio group and iso-prop
  • Y 1 is an alkyl group, in the general formula (1), Y 1 is preferably a methyl group.
  • Y 1 when Y 1 is an alkyl group and dc is an integer of 2 or more, Y 1 may be bonded to each other to form a cyclic structure via an M 1 atom. That is, a plurality of Y 1 may be bonded to form a ring containing M 1 atom.
  • examples of the alkyl chain forming the ring include a methylene group, an ethylene group, and a propylene group, that is, an alkylene group having 1 to 3 carbon atoms.
  • the alkyl chain forming the ring is preferably an ethylene group.
  • the ring containing M 1 atom is specifically a 4-membered ring to a 6-membered ring.
  • examples of the compound represented by the general formula (1) include a compound represented by the following general formula (11).
  • M 1 , a, c, d, and e are the same as M 1 , a, c, d, and e in the general formula (1), respectively.
  • R 3 represents a linear or branched alkyl group having 1 to 3 carbon atoms which may have a substituent.
  • each of the plurality of R 3 s independently represents a linear or branched alkyl group having 1 to 3 carbon atoms which may have a substituent, or a single bond.
  • a plurality of R 3 may be bonded to each other to form a ring containing an M 1 atom, and the portion constituting the ring does not contain a sulfur atom.
  • R 3 represents a linear or branched alkyl group having 1 to 3 carbon atoms which may have a substituent.
  • R 3 represents a linear or branched alkyl group having 1 to 3 carbon atoms which may have a substituent.
  • Several R ⁇ 3 > may be the same group, and the group from which all or one part differs may be sufficient.
  • a plurality of R 3 may be bonded to each other to form a ring containing the atomic group —SM 1 —S—. In this case, the sulfur atom is only directly bonded to the M 1 atom. That is, of the R 3, the parts constituting the ring contains no sulfur atom.
  • R 3 when R 3 does not form a ring, specific examples of R 3 include a methyl group, an ethyl group, a propyl group, and an isopropyl group, that is, an alkyl group having 1 to 3 carbon atoms.
  • a ring containing —M 1 —S— is formed, and the alkyl chain forming the ring is an alkylene group having 1 to 3 carbon atoms.
  • the ring containing M 1 atom is preferably a 4-membered ring to a 6-membered ring.
  • the ring containing the M 1 atom is a 4-membered ring, one of the two R 3 is specifically a single bond.
  • R 3 forms a ring, the following compound represented by formula (12) can be exemplified.
  • a and M 1 are the same as those in the general formula (11)). More specifically, when no ring is formed, R 3 is a methyl group. When a ring is formed, the alkyl chain forming the ring is preferably an ethylene group.
  • the compound represented by the general formula (1) as described above is obtained by a reaction between a halide represented by the following general formula (13) and a compound represented by the general formula (14).
  • the compound represented by the general formula (13) is available as an industrial raw material or a research reagent. Further, the compound represented by the general formula (14) is produced, for example, according to the production method described in JOURNAL OF THE CHEMICAL SOCIETY, 1960, pages 2660 to 2665.
  • the above reaction may be performed without a solvent, or may be performed in the presence of an organic solvent inert to the reaction.
  • Such a solvent is not particularly limited as long as it is inert to the reaction, and is a hydrocarbon solvent such as petroleum ether, hexane, benzene, toluene, xylene, mesitylene; Ether solvents such as diethyl ether, tetrahydrofuran, diethylene glycol dimethyl ether; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone; Ester solvents such as ethyl acetate, butyl acetate, amyl acetate; Chlorine-containing solvents such as methylene chloride, chloroform, chlorobenzene, dichlorobenzene; Aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone, dimethyl sulfoxide; Examples include sulfur-containing solvents such as tetrahydrothiophene
  • the reaction time is influenced by the reaction temperature, but is usually from several minutes to 100 hours.
  • the amount is not particularly limited, the use of the compound represented by the general formula (14) is usually used with respect to 1 mol of the halogen atom contained in the compound represented by the general formula (13).
  • the amount is 0.01 mol or more and 100 mol or less. Preferably, it is 0.1 mol or more and 50 mol or less, More preferably, it is 0.5 mol or more and 20 mol or less.
  • the reaction may be performed without a catalyst, or may be performed in the presence of a catalyst.
  • a base In order to carry out the reaction efficiently, it is preferable to use a base.
  • examples of such base include pyridine, triethylamine, dimethylaniline, diethylaniline, 1,8-diazabicyclo [5,4,0] -7-undecene and the like.
  • the general formula (13) and the general formula (14) are reacted.
  • the general formula (14) and ethanetanedithiol are added dropwise to the general formula (13).
  • ethane tandithiol is added dropwise to a product obtained by reacting the general formula (13) and the general formula (14).
  • the polymerizable composition contains a compound represented by the general formula (1).
  • the polymerizable composition contains a compound represented by the general formula (1).
  • the compounding quantity of the compound shown to the said General formula (1) in polymeric composition may be 1% by weight or more.
  • the polymerizable composition of the present invention includes a thiol compound, an isocyanate compound, an episulfide compound (epithio compound), an epoxy compound, a nonmetallic thietane compound, a metal thietane compound, (meth). At least one of an acrylate compound, a vinyl compound, and an oxetane compound may be included.
  • the polymerizable composition includes the compound represented by the general formula (1) and a thiol compound, an epoxy compound, an epithio compound, or a thietane compound, the mechanical properties and hue of the resulting resin are further improved. Can be improved.
  • the thiol compound, the epoxy compound, the epithio compound, the nonmetallic thietane compound, and the metal thietane compound will be described with specific examples.
  • the priority order of the functional group when the component of the polymerizable composition in the present invention has a plurality of functional groups is as follows.
  • the thiol compound used in the polymerizable composition is a compound containing one or more thiol groups (SH groups) in the molecule.
  • SH groups thiol groups
  • the polymerizable composition contains the compound represented by the general formula (1), any compound having any structure can be used as the thiol compound as long as it is compatible with the compound represented by the general formula (1). it can.
  • thiol compound specifically, as the monovalent thiol compound, methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, octyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan, hexadecyl mercaptan, octadecyl mercaptan, cyclohexyl mercaptan, Benzyl mercaptan, ethylphenyl mercaptan, 2-mercaptomethyl-1,3-dithiolane, 2-mercaptomethyl-1,4-dithiane, 1-mercapto-2,3-epithiopropane, 1-mercaptomethylthio-2,3- Epithiopropane, 1-mercaptoethylthio-2,3-epithiopropane, 3-mercaptothie
  • polyvalent thiol (polythiol) compounds include 1,1-methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2 -Propanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3, 4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, 1,1-bis (mercaptomethyl) cyclohexane, thiomalic acid bis (2-mercaptoethyl ester), 2,3-dimercapto- 1-propanol (2-mercaptoacetate), 2,3-dimercap -1
  • thiol compounds it is preferable to select an aliphatic thiol compound rather than an aromatic one in consideration of the optical properties of the resulting resin, particularly the Abbe number. Further, in view of optical properties, particularly refractive index requirements, it is even more preferable to select a compound having a sulfur atom in addition to a thiol group such as a sulfide bond and / or a disulfide bond. From the viewpoint of improving the three-dimensional crosslinkability in consideration of the heat resistance of the resulting resin, it is particularly preferable to select one or more thiol compounds having a polymerizable group such as an epithio group or a thietanyl group or compounds having three or more thiol groups. .
  • Preferred thiol compounds from the above viewpoints include 1-mercapto-2,3-epithiopropane, 1-mercaptomethylthio-2,3-epithiopropane, 1-mercaptoethylthio-2,3-epithiopropane, 3 -Mercaptothietane, 2-mercaptothietane, 3-mercaptomethylthiothietane, 2-mercaptomethylthiothietane, 3-mercaptoethylthiothietane, 2-mercaptoethylthiothietane, 2,5-bis (mercaptomethyl) 1,4-dithiane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4, 7-dimercaptomethyl-1,11-dimercapto-3,6,9-tri
  • the thiol compound is 3-mercaptothietane, 1,2-ethanedithiol, 4-mercaptomethyl-1,8. -Consisting of dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane and 2,5-bis (mercaptomethyl) -1,4-dithiane One or more selected from the group.
  • an isocyanate compound may be further blended in the polymerizable composition in addition to the thiol compound.
  • the mechanical properties and the like may be further improved by adding an isocyanate compound.
  • the isocyanate compound used here is not particularly limited, but a polyisocyanate compound having a plurality of isocyanate groups is preferable, and a diisocyanate compound is more preferable.
  • a polyisocyanate compound having a plurality of isocyanate groups is preferable, and a diisocyanate compound is more preferable.
  • the polymerizable composition of the present invention may contain an epoxy compound and / or an epithio compound.
  • the epoxy compound and the epithio compound are compounds different from the compound represented by the general formula (1), each containing one or more epoxy groups and epithio groups in the molecule.
  • the epoxy compound and the epithio compound may be any compound having any structure as long as it is compatible with the compound represented by the general formula (1).
  • the epoxy group and / or the epithio group are combined. It is a compound containing two or more.
  • a phenolic epoxy compound for example, bisphenol A glycidyl ether, bisphenol F glycidyl ether obtained by a condensation reaction between a polyhydric phenol compound such as bisphenol A or bisphenol F and an epihalohydrin compound; Alcohol-based epoxy compounds obtained by condensation of polyhydric alcohol compounds such as hydrogenated bisphenol A, hydrogenated bisphenol F, and cyclohexanedimethanol with epihalohydrin compounds (for example, hydrogenated bisphenol A glycidyl ether, hydrogenated bisphenol F glycidyl ether) And other alcohol-based epoxy compounds such as ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, trimethylolpropane triglycidyl ether; Glycidyl ester-based epoxy compounds such as 3,4-epoxycyclohexylmethyl
  • aliphatic polyvalent epoxy compounds such as vinylcyclohexene diepoxide such as 4-vinyl-1-cyclohexane diepoxide.
  • Specific examples of the sulfide group-containing epoxy compound and the ether group-containing epoxy compound include bis (2,3-epoxypropyl) sulfide, bis (2,3-epoxypropyl) disulfide, bis (2,3-epoxypropylthio).
  • phenolic epoxy compounds such as bis (2,3-epoxypropyl) disulfide, 4-vinyl-1-cyclohexane diepoxide, bisphenol A glycidyl ether, bisphenol F glycidyl ether, and the like;
  • Alcohol-based epoxy compounds such as hydrogenated bisphenol A glycidyl ether, hydrogenated bisphenol F glycidyl ether, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, trimethylolpropane triglycidyl ether ;
  • Glycidyl ester epoxy compounds such as 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate and 1,2-hexahydrophthalic acid diglycidyl ester;
  • Examples include amine-based epoxy compounds such as is
  • the epoxy compound is more preferably bis (2,3-epoxypropyl) disulfide, 1,4-cyclohexanedimethanol diglycidyl ether, bisphenol A glycidyl ether, bisphenol F glycidyl ether, ethylene glycol diglycidyl ether, neopentyl glycol disulfide. Glycidyl ether, trimethylolpropane triglycidyl ether, and isocyanuric acid triglycidyl ether. More preferred are 1,4-cyclohexanedimethanol diglycidyl ether and bisphenol F glycidyl ether.
  • epithio compound examples include bis (1,2-epithioethyl) sulfide, bis (1,2-epithioethyl) disulfide, bis (epithioethylthio) methane, bis (epithioethylthio) benzene, and bis [4 -Epithioethylthio compounds such as (epithioethylthio) phenyl] sulfide, bis [4- (epithioethylthio) phenyl] methane; Bis (2,3-epithiopropyl) sulfide, bis (2,3-epithiopropyl) disulfide, bis (2,3-epithiopropylthio) methane, 1,2-bis (2,3-epithiopropyl) Thio) ethane, 1,2-bis (2,3-epithiopropylthio)
  • Aromatic 2, 3-epithiopropylthio compounds Compounds having one epithio group such as ethylene sulfide, propylene sulfide, mercaptopropylene sulfide, mercaptobutene sulfide, epithiochlorohydrin; Bis (2,3-epithiopropyl) ether, bis (2,3-epithiopropyloxy) methane, 1,2-bis (2,3-epithiopropyloxy) ethane, 1,2-bis (2, 3-epithiopropyloxy) propane, 1,3-bis (2,3-epithiopropyloxy) propane, 1,3-bis (2,3-epithiopropyloxy) -2-methylpropane, 1,4 -Bis (2,3-epithiopropyloxy) butane, 1,4-bis (2,3-epithiopropyloxy) -2-methylbutane, 1,3-bis (2
  • preferred compounds are bis (1,2-epithioethyl) sulfide, bis (1,2-epithioethyl) disulfide, bis (2,3-epithiopropyl) sulfide, bis (2,3-epithio).
  • Propylthio) methane and bis (2,3-epithiopropyl) disulfide and more preferred compounds are bis (1,2-epithioethyl) sulfide, bis (1,2-epithioethyl) disulfide, bis (2,3- Epithiopropyl) sulfide and bis (2,3-epithiopropyl) disulfide. Further more preferred compounds are bis (2,3-epithiopropyl) sulfide and bis (2,3-epithiopropyl) disulfide.
  • the epoxy compound and / or epithio compound can be used either alone or in combination, and the amount ratio is not particularly limited. It is also possible to use a plurality of different epoxy compounds that are different from each other or different epithio compounds that are different from each other. However, in order to obtain a high refractive index resin, it is preferable to use an epithio compound.
  • Non-metallic thietane compound contains one or more thietanyl groups in the molecule.
  • the nonmetallic thietane compound may be any compound having any structure as long as it is compatible with, for example, the compound represented by the general formula (1).
  • the compound contains at least two thietanyl groups. It is.
  • thietane compounds such as bisthietanyl sulfide, bis (thietanylthio) methane, 3-(((thietanylthio) methylthio) methylthio) thietane: Examples thereof include polysulfide-type thietane compounds such as bisthietanyl disulfide, bisthietanyl trisulfide, bisthietanyl tetrasulfide, and bisthietanyl pentasulfide.
  • nonmetallic thietane a compound represented by the following formula (15) (1,3-bis (thietanylthio) -2propanol may be used.
  • exemplary compounds it is preferable to select one or more selected from the group consisting of bisthietanyl disulfide, bisthietanyl tetrasulfide, bis (thietanylthio) methane, and 3-(((thietanylthio) methylthio) methylthio) thietane. .
  • preferred compounds are bisthietanyl sulfide, bis (thietanylthio) methane, bisthietanyl disulfide, and bisthietanyl tetrasulfide, and more preferred compounds are bisthietanyl disulfide.
  • the thiol compound is 3-mercaptothietane, 1,2-ethanedithiol, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane and 2,5-bis (mercaptomethyl)
  • the epoxy compound is bis (2,3-epoxypropyl) disulfide, ethylene glycol diglycidyl ether, isocyanuric acid triglycidyl ether, neopentyl glycol diglycidyl Ether, 1,4-cyclohexanedimethanol diglycidyl ether, tri
  • tyrol 2-ethoxypropyl
  • Metal thietan As a compound contained in the polymerizable composition in the present invention, for example, a metal thietane compound represented by the following general formula (3) may be included.
  • This metal thietane compound is a compound containing a thietane group and a specific metal atom in the molecule.
  • the compound represented by the following general formula (3) will be described as an example.
  • This polymerizable composition is used, for example, as a material for optical components.
  • M 2 is a metal atom.
  • X 3 and X 4 are each independently a sulfur atom or an oxygen atom.
  • R 2 is a divalent organic group.
  • m is 0 or an integer of 1 or more.
  • n is the valence of M, and p is an integer of 1 or more and n or less.
  • q is 0 or an integer of 1 to n-2.
  • Y 2 is a monovalent or divalent group, and T is an inorganic or organic group.
  • a plurality of Y 2 may be bonded to each other to form a ring containing the metal atom M 2 .
  • npq 1 or 2
  • Y 2 is a divalent group.
  • the plurality of T are each independently an inorganic or organic group.
  • the polymerizable composition in the present invention may contain one type of compound as the metal thietane compound represented by the general formula (3) or may contain a plurality of different compounds.
  • the metal thietane compound may include a compound in which M 2 is Sb (antimony) or Sn (tin) in the general formula (3).
  • a metal atom M 2 may contain a plurality of different compounds.
  • the polymerizable composition may include, for example, a compound in which M 2 is Sb and a compound in which M 2 is Sn in the general formula (3) as a metal thietane compound.
  • X 3 and X 4 in the general formula (3) are sulfur atoms.
  • Y 2 is the same as Y 1
  • R 2 is the same as R 1 .
  • M 2 is Sn, specifically as a metal thietane compound, Alkylthio (thietanylthio) tin such as methylthiotris (thietanylthio) tin, ethylthiotris (thietanylthio) tin, propylthiotris (thietanylthio) tin, isopropylthiotris (thietanylthio) tin; Bis (alkylthio) bis (thietanylthio) such as bis (methylthio) bis (thietanylthio) tin, bis (ethylthio) bis (thietanylthio) tin, bis (propylthio) bis (thietanylthio) tin, bis (isopropylthio) bis (thietanylthio) tin Tin; Ethylthio (methylthiotris (thietanylthio) t
  • preferred compounds include methylthiotris (thietanylthio) tin, bis (thietanylthio) dithiastannetane, bis (thietanylthio) dithiastannolane, bis (thietanylthio) dithiastanninane, bis (thietanylthio) tri Thiastannocan, methyltris (thietanylthio) tin, and tetrakis (thietanylthio) tin.
  • a still more preferred compound is tetrakis (thietanylthio) tin.
  • Alkylthio (thietanylthio) antimony such as methylthiobis (thietanylthio) antimony, ethylthiobis (thietanylthio) antimony, propylthiobis (thietanylthio) antimony, isopropylthiobis (thietanylthio) antimony;
  • Alkylthiotetra (thietanylthio) antimony such as methylthiotetra (thietanylthio) antimony, ethylthiotetra (thietanylthio) antimony, propylthiotetra (thietanylthio) antimony, isopropylthiotetra (thietanylthio) antimony;
  • Bis (alkylthio) (thietanylthio) antimony such as bis (methylthio) (thietanylthio) antimony
  • Tris (alkylthio) bis (thietanylthio) such as tris (methylthio) bis (thietanylthio) antimony, tris (ethylthio) bis (thietanylthio) antimony, tris (propylthio) bis (thietanylthio) antimony, tris (isopropylthio) bis (thietanylthio) antimony Antimony; Tetra (alkylthio) (thietanylthio) antimony such as tetra (methylthio) (thietanylthio) antimony, tetra (ethylthio) (thietanylthio) antimony, tetra (propylthio) (thietanylthio) antimony, tetra (isopropylthio) (thietanylthio) antimony; Ethylthio (methylthio) (thietanylthio) antimony,
  • preferred compounds include methylthiobis (thietanylthio) antimony, thietanylthiodithiastybetane, thietanylthiodithiathiastyborane, thietanylthiodithiastybinane, bis (thietanylthio) trithiastybocan, methylbis (thietanylthio).
  • Antimony and tris (thietanylthio) antimony is tris (thietanylthio) antimony.
  • n, m, p, X 3 , R 2 , X 4 , M 2 , Y 2 are n, m, p, X 3 , R 2 , X 4 in general formula (3). , M 2 and Y 2
  • the metal thietane compound represented by the general formula (16) typically has a halide containing a metal atom represented by the following general formula (17) and a thietane group represented by the following general formula (18). Produced by reaction with hydroxy or thiol compounds.
  • n, p, M 2 and Y 2 are the same as n, p, M 2 and Y 2 in the general formula (16), respectively, and Z represents a halogen atom.
  • the metal thietane compound represented by the general formula (16) can be produced by a method other than the method using a metal halide.
  • the metal thietane compound represented by the general formula (16) can also be produced by reacting a compound represented by the general formula (18) using a metal oxide or metal amidated compound as a raw material.
  • the compound represented by the general formula (17) is available as an industrial raw material or a research reagent.
  • the compound represented by the general formula (18) is a known compound, and is produced, for example, according to the method described in Patent Document 2 (Japanese Patent Laid-Open No. 2003-327583).
  • reaction of the halide represented by the general formula (17) and the hydroxy compound or thiol compound having a thietane group represented by the general formula (18) may be performed without a solvent, or is inert to the reaction. May be carried out in the presence of a solvent.
  • Such a solvent is not particularly limited as long as it is inert to the reaction, and is a hydrocarbon solvent such as petroleum ether, hexane, benzene, toluene, xylene, mesitylene; Ether solvents such as diethyl ether, tetrahydrofuran, diethylene glycol dimethyl ether; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone; Ester solvents such as ethyl acetate, butyl acetate, amyl acetate; Chlorine-containing solvents such as methylene chloride, chloroform, chlorobenzene, dichlorobenzene; Aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone, dimethyl sulfoxide; Examples include sulfur-containing solvents such as tetrahydrothiophene
  • reaction temperature of the compound represented by the general formula (17) and the compound represented by the general formula (18) is not particularly limited, but is usually in the range of ⁇ 78 ° C. or higher and 200 ° C. or lower, preferably -78 ° C to 100 ° C.
  • reaction time is affected by the reaction temperature, but is usually from several minutes to 100 hours.
  • the amount is not particularly limited, but the use of the compound represented by the general formula (18) is usually based on 1 mol of the halogen atom contained in the compound represented by the general formula (17).
  • the amount is 0.01 mol or more and 100 mol or less. Preferably, it is 0.1 mol or more and 50 mol or less, More preferably, it is 0.5 mol or more and 20 mol or less.
  • a basic compound is used as a scavenger for the generated hydrogen halide in order to efficiently perform the reaction. It is preferable.
  • Examples of such basic compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, magnesium hydroxide, and calcium hydroxide.
  • Inorganic bases; and organic bases such as pyridine, triethylamine, dimethylaniline, diethylaniline, 1,8-diazabicyclo [5,4,0] -7-undecene.
  • the metal thietane compound represented by the general formula (3) is a polymerizable compound.
  • the polymerizable composition of the present invention contains the compound represented by the above formula (1) and the above general formula (3) as the polymerizable compound, and the polymerizable compound represented by the above general formula (3). It may be mainly composed of a metal thietane compound.
  • the polymerizable compound in the polymerizable composition of the present invention may be mainly composed of a metal thietane compound represented by the general formula (5).
  • the polymerizable compound in the polymerizable composition of the present invention contains the metal thietane compound represented by the general formula (3)
  • other polymerization May contain a sexual compound.
  • the polymerizable compound in the polymerizable composition of the present invention may contain other polymerizable compounds in addition to the metal thietane compound represented by the general formula (5).
  • Examples of other polymerizable compounds contained in the polymerizable composition in the present invention include various known polymerizable monomers or polymerizable oligomers, such as (meth) acrylic acid ester compounds, vinyl compounds, oxetane compounds, and the like. .
  • the polymerizable composition of the present invention may further contain a publicly known polymerization catalyst for adjusting the polymerization rate, if necessary.
  • the polymerizable composition of the present invention may contain a bluing agent, if necessary.
  • the bluing agent has an absorption band in the wavelength range from orange to yellow in the visible light region, and has a function of adjusting the hue of the resin. More specifically, the bluing agent contains a substance exhibiting a blue to purple color.
  • the bluing agent used in the polymerizable composition of the present invention is not particularly limited, and specific examples include dyes, fluorescent whitening agents, fluorescent pigments, inorganic pigments, etc. Among those that can be used, it is appropriately selected according to the physical properties required for the lens, the resin hue, and the like. These bluing agents may be used alone or in combination of two or more.
  • dyes are preferred from the viewpoint of solubility in the polymerizable composition and the transparency of the resulting resin.
  • a dye containing one or more dyes selected from blue dyes and violet dyes is preferable, but in some cases, other color dyes may be mixed and used.
  • blue and violet dyes gray, brown, red and orange dyes can also be used.
  • Specific examples of such a combination of bluing agents include a combination of a blue dye and a red dye, and a combination of a violet dye and a red dye.
  • a dye having a maximum absorption wavelength of 520 nm to 600 nm is preferable, and a dye having a maximum absorption wavelength of 540 nm to 580 nm is more preferable.
  • anthraquinone dyes are preferable.
  • dyes include “PS Blue RR”, “PS Violet RC”, “PET Blue 2000”, “PS Brilliant Red HEY”, and “MLP Red V-1” (each trade name of Dystar Japan). ) And the like.
  • the amount of blueing agent used varies depending on the type of monomer, the presence or absence of various additives, the type and amount of additives used, the polymerization method, and the polymerization conditions. Used at a ratio of 0.001 ppm to 500 ppm, preferably 0.005 ppm to 100 ppm, more preferably 0.01 ppm to 10 ppm, based on the total weight of the polymerizable compound contained in the product.
  • the amount of the bluing agent added is too large, the entire lens may become too blue, which may not be preferable. If the amount added is too small, the hue improving effect may not be sufficiently exhibited, which may be undesirable.
  • the method for adding the bluing agent is not particularly limited, and it is desirable to add it to the monomer system in advance.
  • a method of dissolving in the monomer or a high concentration bluing agent is used.
  • Various methods can be employed such as a method of preparing a master solution containing, and diluting the master solution with a monomer using the master solution or another additive.
  • optical properties such as refractive index of resin formed by curing the polymerizable composition, Abbe number, hue, light resistance and weather resistance, heat resistance, impact resistance, hardness, specific gravity, linear expansion coefficient
  • various physical properties such as polymerization shrinkage, water absorption, hygroscopicity, chemical resistance, viscoelasticity, adjustment of transmittance and transparency, viscosity of polymerizable composition, and other handling and handling methods of storage methods
  • resin and handling properties such as purification, washing, heat retention, cold insulation, filtration, reduced pressure treatment, and other commonly used methods for synthesizing organic compounds.
  • compounds added to improve stability such as long-term storage stability, polymerization stability, and thermal stability include compounds such as polymerization retarders, polymerization inhibitors, oxygen scavengers, and antioxidants.
  • Purifying the polymerizable composition is a technique used to improve the transparency of the resin obtained by curing, to improve the hue, or to increase the purity.
  • any known method such as recrystallization, column chromatography (silica gel method, activated carbon method, ion exchange resin method, etc.), extraction, etc. is performed at any timing. In general, it is sufficient that the transparency and hue of a resin obtained by curing a composition generally obtained by purification are improved.
  • the method of washing the polymerizable composition is a technique used to improve the transparency of the resin obtained by curing or to improve the hue, but when the polymerizable composition is synthesized and taken out or after the synthesis
  • a substance that is washed with a polar and / or non-polar solvent at a timing such as after the removal of the resin and inhibits the transparency of the resin for example, an inorganic salt used in synthesizing a polymerizable composition, or a by-product,
  • a method of removing or reducing the amount of ammonium salt and the like can be mentioned.
  • the solvent to be used cannot be generally limited by the polymerizable composition itself to be washed or the polarity of the solution containing the polymerizable composition, but the component to be removed can be dissolved and the polymerizable composition itself to be washed is used. And those that are not compatible with the solution containing the polymerizable composition are preferable, and not only one type but also two or more types may be mixed and used.
  • the components to be removed here vary depending on the purpose and application, but it is preferable to reduce them as much as possible. Usually, good results may be obtained when the content is 5000 ppm or less, more preferably 1000 ppm or less.
  • the method of keeping, cooling, and filtering the polymerizable composition is a technique used to improve the transparency of the resin obtained by curing or to improve the hue, but it is synthesized and taken out. In general, it is performed at a timing such as at the time of extraction or after removal after synthesis.
  • a heat retention method for example, when the polymerizable composition is crystallized during storage and handling becomes worse, the polymerizable composition and the resin obtained by curing the polymerizable composition are heated and dissolved within a range that does not deteriorate the performance. The method of doing is mentioned.
  • the temperature range to be heated and the method of heating and dissolving cannot be generally limited by the structure of the compound constituting the polymerizable composition to be handled, but are usually performed at a temperature within the freezing point + 50 ° C., preferably within + 20 ° C., Examples thereof include a method of mechanically stirring with a stirrable device or a method of moving and dissolving the internal solution by bubbling with an inert gas in the composition. Cooling is usually performed for the purpose of increasing the storage stability of the polymerizable composition. For example, when the melting point of the polymerizable composition is high, the storage temperature should be considered in order to improve the handling property after crystallization. .
  • the cooling temperature cannot be unconditionally limited depending on the structure of the compound constituting the polymerizable composition to be handled and the storage stability, but it is usually necessary to store at or below the temperature at which the stability of the polymerizable composition of the present invention can be maintained. .
  • the polymerizable composition of the present invention is a polymerizable composition used for optical applications, its extremely high transparency is required. Therefore, it is usually preferable to filter the polymerizable composition with a filter having a small pore size.
  • the pore size of the filter used here is usually 0.05 ⁇ m or more and 10 ⁇ m or less. However, in consideration of operability and performance, it is preferably 0.05 ⁇ m or more and 5 ⁇ m or less, more preferably 0.1 ⁇ m or more and 5 ⁇ m or less. is there.
  • the polymerizable composition of the present invention is not an exception, and good results are often obtained by filtration.
  • the temperature at which filtration is performed a more preferable result may be obtained if it is performed at a low temperature near the freezing point. However, if solidification proceeds during filtration, it may be performed at a temperature that does not hinder the filtration operation. There is.
  • the reduced pressure treatment is a technique generally used to remove solvents, dissolved gases, and odors that lower the performance of a resin obtained by curing a polymerizable composition. Since the dissolved solvent may cause a decrease in the refractive index and heat resistance of the resin obtained in general, it should be removed as much as possible.
  • the permissible value of the dissolved solvent cannot be generally limited depending on the structure of the compound constituting the polymerizable composition to be handled and the structure of the dissolved solvent, but is usually preferably 1% or less, more preferably 5000 ppm or less. . It is preferable to remove the dissolved gas from the viewpoint of suppressing the inhibition of the polymerization and the viewpoint of suppressing bubbles from being mixed into the resulting resin.
  • gas such as water vapor by bubbling with a dry gas.
  • it can set according to the structure of the compound which comprises a polymeric composition, the physical property and structure of dissolved gas, and a kind.
  • a compound represented by the general formula (1) and a compound represented by the general formula (3) for example, the general formula (5)
  • a mixture in which the other various polymerizable compounds, polymerization catalysts, additives and the like are charged at once may be heated and dissolved.
  • the obtained polymerizable composition is useful, for example, as a raw material monomer composition for a transparent resin having an extremely high refractive index.
  • the obtained polymerizable composition can be polymerized and cured in accordance with a method for polymerizing a known thietane group-containing compound.
  • the kind and amount of the polymerization catalyst and the like for obtaining the cured resin, and the kind and ratio of the monomer are set according to the structure of the compound constituting the polymerizable composition.
  • an internal mold release agent represented by a surfactant such as an agent or an acidic phosphate ester, a quaternary ammonium salt, or a quaternary phosphonium salt, and an adhesion improver may be added.
  • an internal mold release agent includes what shows the mold release effect among the above-mentioned various catalysts.
  • each additive that can be added differs depending on the type, structure, and effect of each additive, and cannot be unconditionally limited, but is usually 0.001 weight relative to the total weight of the polymerizable composition. % To 10% by weight, preferably 0.01% to 5% by weight. By setting it within these ranges, it is possible to produce a resin that is cured more favorably, and the transparency and optical properties of the resulting resin may be further improved.
  • the resin hue may be improved by adding a hindered amine light stabilizer (HALS) or a phenol, phosphite or thioether antioxidant.
  • HALS hindered amine light stabilizer
  • the addition of a hindered amine light stabilizer (HALS) may significantly improve the resin hue.
  • examples of such a hindered amine light stabilizer (HALS) include ADEKA STAB LA-77, LA-57, LA-52, LA-67, LA-62, LA-68, and LA-63 manufactured by ADEKA Corporation. , LA-87, LA-82 and the like, but are not limited thereto.
  • a resin is obtained by polymerizing the polymerizable composition.
  • Examples of the polymerization method include various known methods used for producing plastic lenses, and typically, cast polymerization is used.
  • the molding mold described above is composed of, for example, two molds that are mirror-polished through a gasket made of polyethylene, ethylene-vinyl acetate copolymer, polyvinyl chloride, or the like.
  • the mold is typically a combination of glass and glass, and other molds include glass and plastic plate, glass and metal plate, but are not limited thereto.
  • the molding mold may be a mold in which two molds are fixed with a tape such as a polyester adhesive tape. As needed, you may perform well-known processing methods, such as a mold release process, with respect to a casting_mold
  • the polymerization temperature is influenced by the polymerization conditions such as the type of polymerization initiator and is not limited, but is usually ⁇ 50 ° C. or higher and 200 ° C. or lower, preferably ⁇ 20 ° C. It is 170 degreeC or less, More preferably, it is 0 degreeC or more and 150 degrees C or less.
  • the polymerization time is influenced by the polymerization temperature, but is usually 0.01 hours or more and 200 hours or less, preferably 0.05 hours or more and 100 hours or less. Moreover, it is also possible to carry out polymerization by combining several temperatures by performing constant temperature, temperature increase, temperature decrease or the like as necessary.
  • the polymerizable composition of the present invention can also be polymerized by irradiating an active energy ray such as an electron beam, an ultraviolet ray or a visible ray.
  • an active energy ray such as an electron beam, an ultraviolet ray or a visible ray.
  • a radical polymerization catalyst or a cationic polymerization catalyst that initiates polymerization by active energy rays is used as necessary.
  • the obtained resin may be annealed as necessary after curing. If necessary, surface polishing, antistatic treatment, hard coat treatment, non-reflective coating treatment, dyeing treatment, dyeing treatment, antireflection, high hardness, wear resistance improvement, antifogging or fashionability.
  • Various known physical or chemical treatments such as light treatment (for example, photochromic lens formation treatment) may be performed.
  • the resin obtained by polymerizing the polymerizable composition of the present invention has high transparency, good heat resistance and mechanical strength, and has a high refractive index, such as a plastic lens. It is useful as a resin used for optical parts.
  • optical components include various plastic lenses such as eyeglass lenses for correcting vision, lenses for imaging devices, Fresnel lenses for liquid crystal projectors, lenticular lenses, and contact lenses; Sealing material for light emitting diode (LED); Optical waveguide; Optical adhesive used for bonding optical lenses and optical waveguides; Anti-reflective film used for optical lenses; Examples thereof include a transparent coating or a transparent substrate used for liquid crystal display device members such as a substrate, a light guide plate, a film and a sheet.
  • Example 1 tris (2,3-epithiopropylthio) antimony (III) (a compound represented by the following formula (21)) was synthesized.
  • Mercaptopropylene sulfide (3.2 g, 0.03 mol) synthesized in Reference Production Example 3 was dissolved in dehydrated tetrahydrofuran (150 g) (commercial product (manufactured by Wako Pure Chemical Industries, Ltd.)) and cooled to ⁇ 30 ° C.
  • dehydrated tetrahydrofuran 150 g
  • dehydrated tetrahydrofuran 150 g
  • 2.9 g of dehydrated pyridine 0.036 mol: commercially available product (manufactured by Wako Pure Chemical Industries) was charged and stirred for 10 minutes.
  • a polymerizable composition was prepared using the epithio compound produced in the above production examples or examples, and was cured by polymerizing to obtain a resin.
  • the physical properties of the obtained resin or optical component (lens) were evaluated by the following methods. Appearance: The transparency was confirmed visually. Refractive index, Abbe number: Measured at 20 ° C. using a Purfrich refractometer.
  • Example 2 Under room temperature (25 ° C.), 0.38 g of the pale yellow oil produced in Example 1 was weighed in a glass beaker, and 1.12 g of the compound produced in Reference Production Example 1 was added and stirred and dissolved. To this solution, 1.5 g of the compound produced in Reference Production Example 2 was further added and stirred and mixed. This was heated to 70 ° C. and stirred to dissolve. Furthermore, after putting in 80 degreeC oven and heating for 14 hours, it heated up to 120 degreeC over 4 hours, and superposed
  • Example 3 At room temperature (25 ° C.), 0.36 g of the pale yellow oil produced in Example 1 was weighed in a glass beaker, and 0.54 g of the compound produced in Reference Production Example 1 was added and stirred and dissolved. To this solution, 2.1 g of the compound produced in Reference Production Example 2 was further added and stirred and mixed. This was heated to 70 ° C. and stirred to dissolve. Furthermore, after putting in 80 degreeC oven and heating for 14 hours, it heated up to 120 degreeC over 4 hours, and superposed
  • the compound represented by the general formula (1) a compound in which M 1 is Sb was used. However, even in the case of Bi, it is understood that the same effect as Sb can be obtained. Yes.
  • Example 3 the compound produced in Reference Production Example 3 was used in place of the compound produced in Example 1. Specifically, it is as follows. Under room temperature (25 ° C.), 0.36 g of the pale yellow oil produced in Reference Production Example 3 was weighed in a glass beaker, and 0.54 g of the compound produced in Reference Production Example 1 was added and stirred and mixed. To this solution, 2.1 g of the compound produced in Reference Production Example 2 was further added and stirred and mixed. This was heated to 50 ° C. and dissolved by stirring. Furthermore, after putting in 80 degreeC oven and heating for 14 hours, it heated up to 120 degreeC over 6 hours, and superposed

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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CN200980129004.7A CN102105478B (zh) 2008-07-28 2009-07-23 化合物、聚合性组合物、树脂及其应用
KR1020117001367A KR101290929B1 (ko) 2008-07-28 2009-07-23 화합물, 중합성 조성물, 수지, 및 그 사용
US13/055,280 US8349996B2 (en) 2008-07-28 2009-07-23 Compound, polymerizable composition, resin, and use of the composition and the resin
JP2010522604A JP5442614B2 (ja) 2008-07-28 2009-07-23 化合物、重合性組成物、樹脂、およびその使用
EP09802669.3A EP2311845B1 (de) 2008-07-28 2009-07-23 Verbindung, polymerisierbare zusammensetzung, harz sowie anwendung der zusammensetzung und des harzes

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JP2018059014A (ja) * 2016-10-07 2018-04-12 三井化学株式会社 チエタニル化合物、当該化合物を含む重合性組成物およびその用途

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WO2011105014A1 (ja) * 2010-02-24 2011-09-01 三菱瓦斯化学株式会社 硬化性樹脂組成物

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EP2311845B1 (de) 2013-09-25
EP2311845A4 (de) 2012-07-11
CN102105478A (zh) 2011-06-22
CN102105478B (zh) 2014-11-05
US20110130516A1 (en) 2011-06-02
US8349996B2 (en) 2013-01-08
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